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Issue 26, 2008
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Nucleophilic substitution reactions of the tricyclic triphosphorus cage P3(CBut)2: a novel route to polyphosphorus phosphenium complexes

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Abstract

Substitution of Cl in the tricyclic triphosphorus cage Cl(P1)-P3(CBut)2 by a range of both anionic and neutral nucleophiles has been investigated. With anionic nucleophiles, reaction with fluoride and hydride anion was shown to afford F(P1)-P3(CBut) and H(P1)-P3(CBut)2 respectively. Subsequent deprotonation of the latter results in the formation of the aromatic anion [1,2,4-P3(CBut)2]. With neutral nucleophiles, addition of either PMe3 or PEt3 to Cl(P1)-P3(CBut)2 in the presence of TlOTf results in the formation of the phosphine–phosphenium complexes [(R3P(P1)-P3(CBut)2][OTf] (R = Me or Et): the structure of the methyl-substituted compound was determined by a single crystal X-ray diffraction study. The phosphine ligand in these complexes is extremely labile and addition of I2 to [(Me3P(P1)-P3(CBut)2]+ results in the formation of I(P1)-P3(CBut)2.

Graphical abstract: Nucleophilic substitution reactions of the tricyclic triphosphorus cage P3(CBut)2: a novel route to polyphosphorus phosphenium complexes

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Publication details

The article was received on 17 Jan 2008, accepted on 27 Feb 2008 and first published on 03 Apr 2008


Article type: Paper
DOI: 10.1039/B800864G
Citation: Dalton Trans., 2008,0, 3422-3428
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    Nucleophilic substitution reactions of the tricyclic triphosphorus cage P3(CBut)2: a novel route to polyphosphorus phosphenium complexes

    C. E. Willans, C. Fish, M. Green, R. J. Kilby, J. M. Lynam, C. A. Russell and A. C. Whitwood, Dalton Trans., 2008, 0, 3422
    DOI: 10.1039/B800864G

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